O-(n-alkoxy-benzimidoyl)-(thiono) phosphoric(phosphonic) acid esters

ABSTRACT

O-(N-alkoxy-benzimidoyl)-(thiono)phosphoric (phosphonic) acid esters of the general formula   IN WHICH R and R2 each is an alkyl radical of one to six carbon atoms, R1 is an alkyl or alkoxy radical of one to six carbon atoms, X is an oxygen or sulfur atom, N IS AN INTEGER FROM 0 TO 5, AND Y is a halogen atom, an alkyl radical of one to four carbon atoms or a nitro group, WHICH POSSESS INSECTICIDAL, AND ACARICIDAL PROPERTIES.

United States Patent 1 1 Lorenz et a1.

1 11 3,760,041 1 Sept. 18, 1973 Bayer Aktiengesellschaft, Wupertal-Elberfeld, all of Germany [22] Filed: Oct. 20, 1971 [21] Appl. No; 191,072

[30] Foreign Application Priority Data Oct. 26, 1970 Germany P 20 52 379.4

[52] US. Cl 260/944, 260/973, 424/211 [51] Int. Cl C071 9/08, C07f 9/16, C07f 9/40 [58] Field of Search 260/944, 945

[56] References Cited UNITED STATES PATENTS 3,597,508 8/1971 Richter et a1 260/944 FOREIGN PATENTS OR APPLICATIONS Germany 260/944v OTHER PUBLICATIONS Hilgetag et a1. Chemical Abstracts, 63 page 7037 (1965).

Primary Examiner--Lewis Gotts Assistant Examiner-Richard L. Raymond Attorney-Burgess et a1.

[57] ABSTRACT O-(N-alkoxy-benzimidoyl)-(thiono)phosphoric (phosphonic) acid esters of the general formula N-O R in which R and R each is an alkyl radical of one to six carbon atoms, R is an alkyl or alkoxy radical of one to six carbon atoms, X is an oxygen or sulfur atom, n is an integer from 0 to 5, and Y is a halogen atom, an alkyl radical of one to four carbon atoms or a nitro group, which possess insecticidal, and acaricidal properties.

7 Claims, No Drawings 1 -(N-ALKOXY-BENZIMIDOYL)-(THIONO) PHOSPHORIC(PHOSPHONIC) ACID ESTERS The present invention relates to and has for its objects the provision of particular new O-(N-alkoxybenzimi'doyll-(thiono)phosphoric(phosphonic) acid esters, i.e. O,()-dialkoxy-0-(N-alkoxy-benzimidoyl) phosphoric acid esters optionally substituted on the benzene ring with up to five halogen, alkyl and/or nitro radicals, the corresponding alkanephosphonic acid esters, and their thiono analogues, which possess insecticidal and 'a'caricidal properties, active compositions in the form 'of mixtures of such compounds with solid and liquid di'spersible carrier vehicles, and methods for producing such compounds and for using such compounds in a new way especially for combating pests, e. g. insects and acarids, with other and further objects becoming apparent from a study of the within specification and accompanying examples.

it is known from German Published Specification No. l l 4 l ,277 that S-(N-alkylbenzimidoyl)-(thiono)thiolphosphoric acid esters, such as 0,0-diethyl-S-(N- methyl-benzimidoyl)-thionothiolphosphoric acid ester (Compound A), exhibit an insecticidal and acaricidal activity. l

The present invention provides, as new compounds, the 0-(N-alkox'y-benzimidoyl) (thiono)phosphoric(- phosphonic) acid esters of the general formula ii is an integer from 0 to 5, and Y is a halogen atom, an alkyl radical to one to four carbon atoms or a nitro group.-

These new compounds have been found to possess strong insecticidal and acaricidal (including tickicidal) properties. 3 g

The present invention also provides a process for the preparation of a compound of the formula (1) above,

in which an N-alkoxy-benzhydroxarnic acid derivativeof the general formula is reacted, in the form of an alkali 'metal, alkaline earth metal or ammonium salt thereof or in the presencev of an acid bindi'ng agent, with a (thiono)phosphoric(- phosphonic) acid ester halide of the general formula P-Hal R1 (III) lh whicll females g R; R R X, Y aiid n have the meanings stated a'bbv, and

Hal is a halogen atom, preferably a chlorine atom.

Surprisingly, the 0-(N-alkoxy-benzimidoyl)- (thiono) phosphoric(phosphonic) acid esters of the present invention show a considerably better insecticidal and acaricida] activity than the known S-(N- alkylbenzimidoyl)-(thiono)thiolphosphoric acid esters of analogous constitution and of the same directions of activity. The compounds according to the present invention therefore represent a genuine enrichment of the art.

lt 0,0dimethyl-thionophosphoric acid ester chloride and N-ethoxybenzhydroxamic acid are used as starting materials, the reaction course can be represented by the following equation:

Preferably, in formula (I) as in formulas (II) and (III), R and R each denotes a straight-chain or branched lower alkyl radical with one to four carbon atoms, namely methyl, ethyl, nor isopropyl or n-, iso-, sec.- or tert.-butyl, R, alternatively denoting a lower alkoxy radical with one to four carbon atoms, namely methoxy, ethoxy, nor iso-propoxy or n-, iso-, sec.- tert.- butoxy; R, preferably denotes methyl, ethyl or nor isopropyl; n is preferably 1, 2 or 3, and each Y, which may be different from one another, is preferably chlorine, bromine, methyl, ethyl or nitro.

As examples of the (thiono )phosphoric(phosphonic) acid ester halides and N-alkoxybenzhydroxamic acid derivatives that maybe used in the preparative process of this invention, there may be metnioned: 0,0-dimethyl-, 0,0-diethyl-, 0,0-dipropyl-, 0,0-diisopropyl-, O-methyl-O-ethyl, O-methyl-O-isopropyl-, 0-ethyl-0-isopropyl-, 0,0-dibutyl-, 0-tert.-butyl-O- methyl-, 0-butyl-0-ethyl-, O-butyl-O-isopropyl and 0,(Ldi-tert.-butyl-phosphoric acid ester chlorides and the corresponding" thiono analogues; 0-methylmethane-, 0-ethyl-propane-, O-isopropyl-ethane, 0- butyl-methane-, O-methyl-isopropane O-methyl: ethane-, 0-ethyl-etharle-, 0-propyl-methane-, O-butyl- 'ethane-, O-tert.-butyl-methan'e-, 0-ethyl-butane-, O-isopropyl-butane-, O-butyI-butane-Oethyl-methanephosphonic acid ester chlorides and the corresponding 5-cliloro-, N=isopropoxy-2-chloro-, N-iso-propoxy-4- amic acid derivatives, be prepared by generally known processes, the latter, for example, being prepared from the corresponding benzhydroxamic acids with alcoholic solutions of potassium hydroxide and an alkyl io dide (Waldstein, Annalen der Chemie, I81, 385) or from benzoyl chlorides and alkoxylamines (Gierke, Annalen der Chemie, 205, 278).

The preparative process is preferably carried out with the use of suitable solvents and diluents. As such, practically all inert organic solvents are suitable, especially aliphatic and aromatic optionally chlorinated hydrocarbons, such as benzene, toluene, xylenes, benzine, methylene chloride, chloroform, carbon tetrachloride and chlorobenzene; ethers, such as diethyl ether, dibutyl ether and dioxane; ketones, for example acetone, and methylethyl, methyl-isopropyl and methyl-isobutyl ketones; and nitriles, such as acetonitrile and propionitrile.

As acid-binding agents, all customary acid-acceptors can be used. Particularly good results have been obtained with alkali metal carbonates and alcoholates, such as sodium and potassium carbonates, methylates and ethylates, as well as with aliphatic, aromatic or heterocyclic amines, for example triethylamine, dimethylamine, dimethylaniline, dimethylbenzylamine and pyridine.

The reaction temperature can be varied within a fairly wide range. In general, the work is carried out at from about to 120C, preferably at from about 40 to 70C.

The reaction is, in general, carried out at normal pressure.

For the carrying out of the process, the starting materials are in most cases used in equimolar amounts. An excess of one or the other of the reactants brings no substantial adavantages. The reaction is preferably carried out in the presence of one of the above-mentioned solvents, as well as in the presence of an acid-acceptor, within the temperature range stated, and the reaction mixture, after several hours stirring optionally with heating is worked up by customary methods.

The compounds according to the invention are in most cases obtained in the form of colorless to slightly yellow-colored, viscous, water-insoluble oils which cannot be distilled without decomposition but can, by so-called slight distillation) that is by prolonged heating at moderately elevated temperatures under reduced pressure, be freed from the last volatile components and in this way be purified. For their characterization, the refractive indexes are especially suitable.

As already mentioned, the new O-(N- alkoxybenzimidoyl)-(thiono )phosphoric(phosphonic) acid esters are distinguished by an outstanding insecticidal and acaricidal effectiveness against crop pests, pests harmful to health and pests of stored products. They' possess a good activity against both sucking and eating insects, and mites (Acarina), but at the same time they exhibit only a very low phytotoxicity. In some cases they are also of interest in the ectoparasite field. For these reasons, the compounds according to the invention may be used with success as pesticides in crop protection and the protection of stored goods, as well as in the hygiene and veterinary fields.

In the course of time, parasitizing Diptera larvae have in various areas become resistant to the agents based on organic phosphorus compounds and carbamates used hitherto as prophylactics, so that the success of treatment is to an increasing extent rendered questionable, In order to ensure an economic livestock husbandry in the infestation areas, there exists therefore an urgent need for agents with which the infestation with blowfly larvae, even of resistant strains, for example of the genus Licilia, can be prevented with certainty. For

example, in Australia the Goondiwindi strain and in South Africa the Alexandria strain of Lucilia cuprina have become to a great extent resistant to the phosphoric acid esters and carbamates used hitherto. The active compounds according to the present invention prove to be equally well efi'ective both against the normally sensitiveand against the resistant blowfly strains in that they show an equally long prophylactic protective duration both against normally sensitive and against resistant blowfly larvae.

To the sucking insects against which the novel compounds may be used, there belong, in the main, aphids (Aphidae) such as the green peach aphid (Myzus persicae), the bean aphid (Daralis fabae), the bird cherry aphid (Rhopalosiphum padi), the pea aphid (Macrosiphum pisi) and the potato aphid (Macrosiphum solanifolii), the currant gall aphid (Crypromyzus korschelli), the rosy apple aphid (Sappaphis mali), the mealy plum aphid (Hyalopterus arundinis) and the cherry black-fly (Myzus cerasi); in addition, scales and mealybugs (Coccina), for example the oleander scale (Aspidiotus hederae) and the soft scale (Lecanium hesperidum) as well as the grape mealybug (Pseudococcus maritimus); thrips (Thysanoptera), such as Hercinothrips femoralis, and bugs, for example the beet bug (Piesma quadrata), the red cotton bug (Dysdercus intermedius), the bed bug (Cimex lectularius), the assassin bug (Rhodnius prolixus) and Chagas bug (Triatoma infesrans) and, further, cicadas, such as Eusc'elis bilobatus and Nephotettix bipunctatus; and the like.

In the case of the biting insects contemplated herein, above all there should be mentioned butterfly caterpillars (Lepidoptera) such as the diamond-back moth (Plutella maculipermis), the gypsy moth (Lymantria dispar), the brown-tail moth (Euproctis chrysorrhoea) and tent caterpillar (Malacosoma neustria); further, the cabbage moth (Mamesrra brassicae) and the cutworm (Agrotis segetum), the large white butterfly (Pieris b rassicae), the small winter moth (Cheimalobia brumata), the green oak tortrix moth (Tortrix viridana), the fall armyworm (Laphygma frugiperda) and cotton worm (Prodenia litura), the ermine moth (Hyponomeuta padella), the Mediterranean flour moth (Ephestia kuhniella) and greater wax moth (Galleria mellonella); and the like.

Also to be classed with the biting insects contemplated herein are beetles (Coleoptera), for example the granary weevil (Sitophilus granarius Calandra granaria), the Colorado beetle (Leptinotarsa decemlineata), the dock beetle (Gastrophysa viridula), the mustard beetle (Phaedon cochleariae), the blossom beetle (Meliget hes aeneus), the raspberry beetle (Byturus tomentosus), the bean weeveil (Bruchidius Acanthoscelides obtectus), the' leather beetle (Dermestes frischi), the khapra beetle (Trogoderma granarium), the flour beetle (Tribolium castaneum), the norther corn billbug (Calandra or Sitrophilus zeamais), the drugstore beetle (Stegobium paniceum), the yellow mealworm (Tenebrio molitor) and the sawtoothed grain beetle (Oryzaephilus surinamensis), and

also species living in the soil for example wireworms (Agriotes spec.) and larvae of the cockchafer (Melolontha melolontha); cockroaches, such as the German cockroach (Blattella germanica), American cockroach (Periplaneta americana), Madeira cockroach (Leucophaea or Rhyparobia maderae), oriental cockroach (Blatta orientalis), the giant cockroach (Blaberus giganteus) and the black giant cockroach (Blaberus fuscus) as well as Henschoutedenia flexivitta; further, Orthoptera, for example the house cricket (Acheta domesticus); termites such as the eastern subterranean termite (Reticulitermes flavipes) and Hymenoptera such as ants, for example the garden ant (Lasius niger); and the like.

The Diptera contemplated herein comprise essentially the flies, such as the vinegar fly (Drosophila melanogaster) the Mediterranean fruit fly (Ceratitis capizata), the house fly (Musca domestica), the little house fly (Fannia canicularis), the black blow fly (Phormia regina) and bluebottle fly (Calliphora eryzhrocephala) as well as the stable fly (Stomoxys calcitrans); further, gnats, for example mosquitoes such as the yellow fever mosquito (Aedes aegypti), the northern house mosquito (Culex pipiens) and the malaria mosquito (Anopheles stephensi); and the like.

With the mites (Acarina) contemplated herein there are classed, in particular, the spider mites (Tetranychidae) such as the two-spotted spider mite (Tetranychus telarius Tetranychus althaeae or Tetranychus urticae) and the European red mite (Paratetranychus pilosus Panonychus ulmi), gall mites, for example the black currant gall mite (Eriophyes ribis) and tarsonemids, for example the broad mite (Hemitarsonemus latus) and the cyclamen mite (Tarsonemus pallidus); finally, ticks, such as the relapsing fever tick (Ornithodorus moubata); and the like.

When applied against pests harmful to health and pests of stored products, particularly flies and mosquitoes, the compounds of this invention are also distinguished by an outstanding residual activity on wood and clay, as well as a good stability to alkali on limed substrates.

in the veterinary field, the compounds according to the invention may be used with success against numerous noxious animal parasites (ectoparasites such 'as arachnids and insects). As ectoparasites contemplated herein, there are mentioned here from the class of the Arachnidea: lxodidae, such as for example the one-host Australian and South American cattle tick 'Boophilus microplus, the one-host American cattle tick Boaphilus annulatus and the one host African cattle tick Boophilus 'decoloratus (in each case, strains normally sensitive to, and strains resistant to, phosphoric acid esters and carbamates), as well as multi-host cattle and sheep ticks of the genera Rhipicephalus (for example Rhipicephalus evertsi, Rhipicephalus appendiculatus, Rhipicephalus simus, Rhipicephalus bursa), Amblyomma (for example Amblyomma hebraeaum), Hyalomma (for example Hyalomma truncatum) and Ixodes (for example lxodes rubicundus); and the like.

As ectoparasites contemplated herein from the class of the insects, there arementioned: mallophagans, for

example the sheep biting louse (Damalinia ovis) and the chicken body louse (Eomenacanthus stramineus); Anoplura for example the short-nosed cattle louse (Haematopinus eurysternus); Diptera for example the sheep ked (Melophagus ovinus) permanently parasitizing on the host) and certain flies (temporarily parasitizing on the host), for example Liperosia irrimns, Liperosia exigua and Musca autumnalis; Diptera larvae (parasitizing in warm-blooded animals) such as blowfly larvae (for example larvae of Lucilia sericata, of Lucilia cuprina (strains normally sensitive to, and strains resistant to, phosphoric acid esters) and of Chrysomyia chloropyga); further larvae of warble flies, for example Hypoderma bovis, as well as screwworm larvae, for example of the genus Cochliomyia macellaria; and the like.

The active compounds according to the instant invention can be utilized, if desired, in the form of the usual formulations or compositions with conventional inert (i.e. plant compatible or herbicidally inert) pesticide diluents or extenders, i.e. diluents, carriers or extenders of the type usable in conventional pesticide formulations or compositions, e.g. conventional pesticide dispersible carrier vehicles such as gases, solutions, emulsions, suspensions, emulsifiable concentrates, spray powders, pastes, soluble powders, dusting agents, granules, etc. These are prepared in known manner, for instance by extending the active compounds with conventional pesticide dispersible liquid diluent carriers and/or dispersible solid carriers optionally with the use of carrier vehicle assistants, e.g. conventional pesticide surface-active agents, including emulsifying agents and/or dispersing agents, whereby, for example, in the case where water is used as diluent, organic solvents may be added as auxiliary solvents. The following may be chiefly considered for use as conventional carrier vehicles for this purpose: Aerosol propellants which are gaseous at normal temperatures and pressures, such as freon; inert dispersible liquid diluent carriers, including inert organic solvents, such as aromatic hydrocarbon (e.g. benzene, toluene, xylene, etc.), halogenated, es pecially chlorinated, aromatic hydro-carbons (e.g. chlorobenzenes, etc.), paraffins (e.g. petroleum and mineral oil fractions), chlorinated aliphatic hydrocarbons (e.g. methylene chloride, etc.), alcohols (e.g.

methanol, ethanol, propanol, butanol, etc.), amines (e.g. ethanolamine, etc.), ethers, ether-alcohols (e.g. glycol monomethyl ether, etc.), amides (e.g. dimethyl formamide, etc.), sulfoxides (e.g. dimethyl sulfoxide, etc.), ketones (e.g. acetone, etc.), and/or water; as well as inert dispersible finely divided solid carriers, such as ground natural minerals (e.g. kaolins, clays, alumina, silica, chalk, i.e. calcium carbonate, talc, attapulgite, montmorillonite, kieselguhr, etc.) and ground synthetic minerals (e. g. highly dispersed silicic acid, silicates, e. g. alkali silicates, etc.); whereas the following may be chiefly considered for use as conventional carrier vehicle assistants, e.g. surface-active agents, for this purpose: emulsifying agents, such as non-ionic and/or anherbicides, fertilizers, growth-regulating agents, etc., if desired, or in the form of particular dosage preparations for specific application made therefrom, such as solutions, emulsions, suspensions, powders, pastes, and granules which are thus ready for use.

As concerns commercially marketed preparations, these generally contemplate carrier composition mixtures in which the active compound is present in an amount substantially between about 0.1-95 percent by weight, and preferably 0.5-90 percent by weight, of the mixture, whereas carrier composition mixtures suitable for direct application or field application generally contemplate those in which the active compound is present in an amount substantially between about 0.0001-I percent, preferably 0.01-l percent, by weight of the mixture. Thus, the present invention contemplates over-all compositions which comprise mixtures of a conventional dispersible carrier vehicle such as (l) a dispersible inert finely divided carrier solid, and/or (2) a dispersible carrier liquid such as an inert organic solvent and/or water preferably including a surface-active effective amount of a carrier vehicle assistant, e.g. a surface-active agent, such as an emulsifying agent and- /or a dispersing agent, and an amount of the active compound which is effective for the purpose in question and which is generally between about 0.0001-95 percent, and preferably 0.01-95 percent, by weight of the mixture.

The active compounds can also be used in accordance with the well known ultra-low-volume process with good success, i.e. by applying such compound if normally a liquid, or by applying a liquid composition containing the same, via very effective atomizing equipment, in finely divided form, e.g. average particle diameter of from 50-100 microns, or even less, i.e. mist form, for example by airplane crop spraying techniques. Only up to at most about a few liters/hectare are needed, and often amounts only up to about 15 to 1000 g/hectare, preferably 40 to 600 g/hectare, are sufficient. In this process it is possible to use highly concentrated liquid compositions with said liquid carrier vehicles containing from about 20 to about 95 percent by weight of the active compound or even the 100 percent active substance alone, e.g. about 20-100 percen by weight of the active compound.

Furthermore, the present invention contemplates methods of selectively killing, combating or controlling pests, e.g. insects and acarids, and which comprises applying to at least one of correspondingly (a) such insects, (b) such acarids, and (c) the corresponding habitat thereof, i.e. the locus to be protected, a correspondingly combative or toxic amount, i.e. an insecticidally or acaricidally effective amount of the particular active compound of the invention alone or together with a carrier vehicle as noted above. The instant formulations or compositions are applied in the usual manner, for instance by spraying, atomizing, vaporizing, scattering, dusting, watering, squirting, sprinkling, pouring, fumigating, clipping of animals, administering perenterally or by injection and the like.

It will be realized, of course, that the concentration of the particular active compound utilized in admixture with the carrier vehicle will depend upon the intended application. Therefore, in special cases it is possible to go above or below the aforementioned concentration ranges.

The unexpected superiority and outstanding activity of the particular new compounds of the present invention are illustrated, without limitation, by the following examples:

EXAMPLE Drosophila Test Solvent: 3 parts by weight acetone Emulsifier: 1 part by weight alkylarylpolyglycol ether To produce a suitable preparation of active compound, part by weight of the active compound is mixed with the stated amount of solvent containing the stated amount of emulsifier, and the concentrate is diluted with water to the desired concentration. I

1 cc of the preparation of the active compound is applied with a pipette to a filter paper disc of 7 cm diameter. The wet disc is placed in a glass vessel containing 50 vinegar flies (Drosophila melanogaster) and covered with a glass plate.

After the specified periods of time, the destruction is determined as a percentage: 100 percent means that all the flies are killed; 0 percent means that none of the flies are killed.

The active compounds, their concentrations, the evaluation times and the degree of destruction can be seen from Table 1:

TABLE 1 (Drosophila test) Active compound Concentration of Degree of active compound destruction in in after 1 day CS--P OCH u 2 0.1 'N-CHa (known) 0.0] 0

a H 0.1 I00 (:-01*(00,11, z 0.01 10 H 0.001 100 N-0 CH: 0.0001 98 fi/o lh 0,1 100 c 0.01 100 H 0.001 100 N-OCH: 0 Cells 0.0001 100 (2) 0.1 100 Q-c-o-mocnm 0.01 100 11 0.001 100 N-O Czlla 0.0001 99 s (1) H 0.! I00 Q-c-o-Hocnh): 0.01 100 0001 100 NO Czm 0.0001 60 fi/C lig,

0.1 100 11 O 0.01 100 Il 2115 0.001 100 NO C m 0.0001 99 -co-i (0 can), 01 100 H 0.01 100 Calls 0.001

ll N-O 0 111 ll %-0-P (0cm (in) 0,1 l()() 01- 0 -1- 01'11 0 0.01 100 ll 0,001 100 0-0-P OCH 100 Q 11 0,01 100 g N-OCH; 0,001 100 r 0,0001 100 -c- H .1 100 Q ILL 0 (0C 0.01 100 OCH3 0.001 100 CH1 0.0001 100 CO-P(OCH:)1 0.1 100 0.01 100 1 N-OCzHs 0 00 00 0.0001 100 1 c- -P 00 H 100 Q1! 0 2 .0! 100 NOCH1 0.001 100 CH3 0,0001

--'COP(OCZH5)1 0'] 100 1| 0.01 100 N-OCzHs 0,001 100 CH: 0,0001

o N- c-0-1 OCH OJ 2 Q ll 1 100 N0CH= 0.001 100 EXAMPLE 2 Phaedon Larvae Test Solvent: 3 parts by weight acetone Emulsifier: 1 part by weight alkylaryl polyglycol ether To produce a suitable preparation of active compound, 1 part by weight of the active compound is mixed with the stated amount of solvent containing the stated amount of emulsifier, and the concentrate is diluted with water to the desired concentration.

Cabbage leaves (Brassica oleracea) are sprayed with the preparation of the active compound until dripping wet and then infested with mustard beetle larvae (Phaedon cochlearia e).

After the specified periods of time, the degree of destruction is determined as a percentage: 100 percent means that all the beetle larvae are killed. 0 percent means that none of the beetle larvae are killed.

The active compounds, the concentration of the active compound, the times of evaluation and the results can be seen from the following Table 2:

TABLE 2 (Phaedon larvae test) Active compound Concentration of Degree of active compound destruction in in afler 3 days l00 lOO lOO I00 A; N-O CzHs (ll I00 1 0.01

[C]; O P (0C 0. mo N() CzHs 0.01 lOO 0.00l I00 OzN- -C-O-l (OCIH); OJ I00 H 0.0] 100 NO cm, 0.001 60 EXAMPLE 3 Myzus Test (Contact Action) Solvent: 3 parts by weight acetone Emulsifier: 1 part by weight alkylarylpolyglycol ether To produce a suitable preparation of active compound, part by weight of the active compound is mixed with the stated amount of solvent containing the stated amount of emulsifier and the concentrate is diluted with water to the desired concentration.

Cabbage plants (Brassica oleracea) which have been heavily infested with peach aphids (Myzus persicae) are sprayed with the preparation of the active compound until dripping wet.

After the specified periods of time, the degree of destruction is determined as a percentage: 100 percent means that all the aphids are killed whereas 0 percent means that none of the aphids are killed.

The active compounds, the concentrations of the active compounds, the evaluation times and the results can be seen from the following Table 3:

TABLE 3 (Myzus test) Active compound Concentration of Degree of active compound destruction in in after I day C-SP 00 H NCH: (known) 0.0! 0

(5) 3 t -c-o 1 (o can):

- H 0.1 100 NO CH3 0.01

n ..C 0.] I00 ll 0.0! N-OCII: 0 cans 0,001 9 (4) S Cglls Ii 0 CzHs 0.l 100 N-OC: s 0.01 t 90 -c1 00 11 Q n 01 I00 NOC2H5 0.01 50 (]J NOC2H5 0.1 100 1 0.01 100 13 c1 I S 02115 l OCzHs 0.1 lOO N-oc1 5 0.01 99 -COP(OCH5)2 N-OCzH5 Q 100 r 0.01 95 (12) i 0.1 100 0,N- c-0-P(oo.m)1 1| 0.001 100 N-o 01m 0.0001 70 14 cn'r'.

0.1 100 ON Q C 0 P 0.01 100 Q0235 0.001 100 N-OC: s 0.000l 90 f, 0.1 100 0,N- C-0P (00am H 0.001 100 N-0 01111 0.0001 40 (26) 0,1 100 2N P(OCH:1)z I] 0,001 100 NOCHa 0,0001 45 EXAMPLE 4 Tetranychus Test Solvent: .3 parts by weight acetone Emulsifier: 1 part by weight alkylarylpolyglycol ether To produce a suitable preparation of active compound, 1 part by weight of the active compound is mixed with the stated amount of solvent containing the stated amount of emulsifier and the concentrate so obtained is diluted with water to the desired concentration.

Bean plants (Phaseolus vulgaris), which have a height of approximately 10-30 cm., are sprayed with the preparation of the activecompound until dripping wet. These bean plantsare heavily infested with spider mites (Tetranychus urticae) in all stages of development.

After the specified periods of time, the effectiveness of the preparation of active compound is determined by counting the dead mites. The degree of destruction thus obtained is expressed as a percentage: I00 percent means that all the spider mites are killed whereas 0 per- .cent means that none of the spider mites are killed.

The active compounds, the concentrations of the active compounds, the evaluation times and the results can be seen from the following Table 4:

TABLE'4 (Tetranychus test) Active compound Concentration of Degree of active compound destruction in in after 2 days N-CH; (known) 0.1 0

I N-O can OzN- -COP\ h 0 01115 N-o C; 5 1

l N-OCH; 0.1 100 Cl 0.01 90 25 Q- -O-flOCHaM N-O cm 100 111- 0.01 100 0,Ntfi01 0 OHM N-O CH1 0.1 100 EXAMPLE 5 LD oo Test Test animals: Sitophilus granarius Solvent: acetone 1 2 parts by weight of the active compound are dissolved in 1000 parts by volume of the solvent. The solution so obtained is diluted with further solvent to the desired concentrations.

2.5 ml of the solution of the active compound are pipetted into a Petri dish. On the bottom of the Petri dish there is a filter paper with a diameter of about 9.5 cm. The Petri dish remains uncovered until the solvent has completely evaporated. The amount of active compound per square meter of filter paper varies with the concentration of the solution of active compound used. 25 test animals are then placed in the Petri dish and it is covered with a glass lid.

The condition of the test animals is observed 3 day after the commencement of the experiments. The destruction is determined as a percentage.

The active compounds, the concentrations of theactive compounds, the test animals and the results can be seen from the following Table 5:

TABLE 5 (LD test) Active compound Concentration of Degree of active compound destruction of the solution in in ll -CO--P ii CH 0.2 100 N() CzHs 0.02 60 i 01 3) S CzHs C T 0.2 100 H O CzHs 0.02 100 NO C21 0.002 l00 Q- -O-Pw c2115):

6 N-O C2H5 0.2 I00 1 0.02 100 (1 0 0.2 100 Dr 0.02 I00 qN- -COP(OC H Q n z 5 2 N--O C2H5 0.02 lOO ll OzN- COP H 0 CzHs 0.2 100 N-O 02115 0.02 100 (fi-0P(OCH3): 01 we (32H5 0.02 [00 Cl 0.002 50 OgN- -COP (OCHJ):

H 0.2 100 NO CzHs 0.02 50 Q- -o-r (00113): 01 100 N-OCzHs 0.02 100 Br 0.002 50 EXAMPLE 6 Mosquito Larvae Test Test insects: Aedes aegypti larvae Solvent: 99 parts by weight acetone Emulsifier: 1 part by weight benzylhydroxydiphenyl polyglycol ether To produce a suitable preparation of active compound, 2 parts by weight of the active compound are dissolved in 1000 parts by volume of the solvent containing the amount of emulsifier stated above. The solution thus obtained is diluted with water to the desired lower concentrations.

The aqueous preparations of the active compounds are placed in glass vessels and about 25 mosquito larvae are then placed in each glass vessel.

After 24 hours, the degree of destruction is determined as a percentage. 100 percent means that all the larvae are killed. 0 percent means that no larvae at all are killed.

The active compounds, the concentrations of the active compounds, the test insects and the results can be seen from Table 6:

TABLE 6 (Mosquito larvae test) Active compound I Concentration of Degree of active compound destruction of the solution in in ppm o-s r 0 0mm N-CHa (known) 10 0 [i OCEH 10 100 Q I 100 N-O CH3 0.1 40

c 0 V H lo 100 N-OCH: O CzHa l 100 52 CO-P (00113):

( C-OI(O 11-1 IO 100 N-OCzHa l v H F K O CzLLa 10 N-O CzHs l 100 i S czHa H COP 10 I00 ll 0 C211; 1 100 N-OCzIIa- 0.1 30

COl OCQH, 3 Q :4 O 10 100 I NO Cali; l lOO Cl 0,! I00 completely evaporated. The amount of active compound per square meter of filter paper varies with the concentration of the solution of active compound used. About 25 test animals are then placed in the Petri dish and it is covered with a glass lid.

The condition of the test animals is periodically observed. The time which is necessary for a 100 percent destruction is determined.

The test animals, the active compounds, the concentrations of the active compounds and the periods of time at which there is a percent destruction can be seen from the following Table 7:

TABLE 7 (LT test for Diptera) Phorodon Test (Contact Action) Solvent: 3 parts by weight acetone Emulsifier: 1 part by weight alkylarylpolyglycol ether To produce a suitable preparation of active compound, 1 part by weight of the active compound is mixed with the stated amount of solvent containing the stated amount of emulsifier, and the concentrate is diluted with water to the desired concentration.

Hop plants (Humulus lupulus) which have been heavily infested with the hop aphid (Phorodon humuli) are sprayed with the preparation of the active compound until dripping wet.

After the specified periods of time, the degree of de struction is determined as a percentage: 100 percent means that all the aphids were killed; percent means that none of the aphids were killed.

The active compounds, the concentrations of the active compounds, the evaluation times and the results can be seen from the following Table 8:

TABLE 8 (Phorodon humuli) Concentration of Active compound Degree of active compound destruction in in after 1 day ;-s 1 0c1rn)g N-CH; (known) 0.02 30 M 0.02 11 OCZH5 0.004 100 N() 211-, 0.0008 98 0.02 100 0.004 100 00 1; 0.0008 100 NOC ll5 0.000l6 100 EXAMPLE 9 Myzus Test (Contact Action) (Resistant) Solvent: 3 parts by weight acetone Emulsifier: 1 part by weight alkylarylpolyglycol ether To produce a suitable preparation of active compound, 1 part by weight of the active compound is mixed with the stated amount of solvent containing the stated amount of emulsifier and the concentrate is diluted with water to the desired concentration.

Cabbage plants (Brassica oleracea) which have been heavily infested with peach aphids (Myzus persicae) are sprayed with the preparation of the active compound until dripping wet.

After the specified periods of time, the degree of destruction is determined as a percentage: 100 percent means that all the aphids are killed whereas 0 percent means that none of the aphids are killed.

The active compounds, the concentrations of the active compounds, the evaluation times and the results can be seen from the following Table 9:

TABLE 9 (Myzus persicae test resistant) Active compound Concentration of Degree of active compound destruction in in after I day CSP 06 H Q 11 z 35 N-CH: (known) 0.02 20 I S C H5 @r- 0 0.02 97 NO C2115 0.004 50 (14) iS/C lls 0.1 100 0.02 99 ll OCzlIr, (1004 93 NO Calls 0.0008 45 EXAMPLE 10 Test with Parasitizing Fly Larvae Solvent: 35 parts by weight ethyleneglycolmonomethyl ether.

Emulsifier: 35 parts by weight nonylphenolpolyglycol ether.

To produce a suitable preparation of active compound, 30 parts by weight of the active substance concerned is mixed with the stated amount of solvent which contains the above mentioned proportion of emulsifier, and the concentrate so obtained is diluted with water to the desired concentration.

Table 10.

EXAMPLE Tick Test Solvent: 35 parts by weight ethyleneglycolmonomethyl ether Emulsifier: 35 parts by weight nonylphenolpolyglycol ether To produce a suitable formulation, 3 parts by weight of the active compound are mixed with 7 parts by weight of the above-mentioned solventfemulsifier mixture, and the emulsion concentrate so obtained is diluted with water to the concentration desired in each case.

Adult, gorged female ticks of the species Boophilus microplus (sensitive and resistant, respectively) are immersed for one minute in these preparations of active compound. After immersion of, in each case, 10 female specimens of the various tick species, they are transferred to Petri dishes, the bottom of which is covered with a correspondingly large filter disc.

After 10 days, the effectiveness of the preparation of active compound is determined by ascertaining the inhibition of egg deposition compared with untreated control ticks. The effect is expressed as a percentage, 100 percent meaning that eggs ceased to be deposited, and percent signifying that the ticks deposited eggs in normal amount.

The active compounds investigated, the concentrations tried, the parasites tested and the findings ob- 20 tained can be seen from the following Table 10.

' TAB LE 10 Concen- Degree of Inhibition of egg tration destruc- Concendeposition in percent of active tion in tration of (Boophilus microplus) compercent active pound (Lucilia compound Ridgeland Biarra Active compound in, ppm. cuprlna) 1n. ppm. strain strain 1 t S 300 H 100 C-OP (OCzHs): N-O C2H5 -CO-P(OCH:): N O 0 H 3) 0 300 H 100 (|iO-P(OC2H5)2 N-O (77H: 3

(4) S C H5 300 H 30 -C--- O-P 3 ll 1 I NOC:H5 OCzHs 5 s 300 H 100 (|%OP(OC2H5)2 NO CH: 1;

(6) S C 2H5 300 100 C- O P 39 ll N-OCHa 0 02m 3 (7) S 300 100 C1 (fi-O-IWOCzHsh NOC2H5 8 300 100 %O- (OC2 5)2 N() (32115 C1 9 300 H 100 -CO1( 2H5)z 30 ll 10 NO CgH C1 (l0) S 300 100 10,000 100 100 H 100 100 s. 000 100 COP(OC:H )2 30 1,000 100 50 ll 10 100 300 50 50 100 50 50 TABLE 10 ('ontinued Concen- Degree of Inhibition of egg tration destruc- Concendeposition in percent of active tion in tration of (Boophilua microplua) compercent active pound (Lucilia compound Rldgcland Biarra Active compound in, ppm. cuprina) iii, p.p.m. strain strain (11) S 300 100 H=c- -o-P can)? 30 N- O C2115 l2 S 300 H 100 O2N- C-OP(OCiH.-;)2 38 N O C 2H5 3 EXAMPLE 12 The active compounds investigated, the concentra- Blowfly Larvae Test on Artificially Infected Sheep tions tried, the parasites tested and the findings obtained can be seen from the following Table l 1:

TABLE 11 [Blowfly larvae test on artificially infected sheep] Concentration of active com- Average pound in duration ppm. of protec before Type of tion in Active compound infection larvae weeks (1) S 1,000 Sensitive 14 I] 1,000 Resistant- 14 COP(0CzHa)2 750 Scnsitive 14 [I 750 Resistant. 14 NOCzH 500 Sensitiv0 14 500 Resistant. 14

(B) 500 Sensitivo (4-14) CHiS-- O"|ll(OC:Hi)i 500 Resistant. 5.6 (2-12) I S CH;

(known) Control Sensitive" 0 (Untreated) Resistant. 0

Solvent: parts by weight ethyleneglycol- EXAMPLE l3 monomethyl ether 40 Emulsifier: 35 parts by weight nonylphenolpolyglycol (her Stinging Fly Test To produce a suitable formulation, 3 parts by weight s w 35 parts b wei ht ethyieneglycolof active compound are mixed with 7 parts of the monomethyl ether abovementioned solvent-emulsifier mixture, and the emulsion concentrate so obtained is diluted with water to the concentration desired in each case.

Groups of sheep with a certain length of wool are dipped in these preparation of active compound. At intervals of 14 days, beginning 14 days after application of the active compound, normally sensitive blowfly larvae and resistant blowfly larvae are implanted at, in each case, 2 body sites behind the shoulder blade and at the level of the points of the hip bones. In addition, blowfly larvae are inserted into incised wounds about 2 cm long (contaminated with a mixture of sheep dung and scraped meat) in the skin of sheep. The sheep are kept at grass during the summer months and in a sheepshed (20C 1 3C; 70 percent relative humidity i 10 percent during the winter months.

Observation of the active compound takes place in each case 48 hours after implantation of the larvae. As the criterion for the in-vivo effect, the length of duration of protection after dipping is taken. The duration of protection is the length of time in which a commencement of infection with the implanted larvae is completely prevented.

Emulsifier: 35 parts by weight nonylphenolpolyglycol ether To produce a suitable formulation, 3 parts by weight of active compound are mixed with 7 parts of the above-mentioned solvent-emulsifier mixture, and the emulsion concentrate so obtained is diluted with water to the concentration desired in each case.

At various times after the treatment, the degree of destruction is determined; percent means that all the flies, and 0 percent denotes that none of the flies, have been killed.

The active compound investigated, the concentrations tried, the parasite tested and the findings obtained can be seen from the following Table 12:

TABLE 12 [Stlngingfly test] Concon- Eflect in percent tratlon (hours after insertion of active of the flies) aftercompound Active compound Parasite in p.p.m. 1 hr. 24 hrs.

(1) S Stomozys calcitrana 1, 000 100 100 I] 100 50 100 C-P(OCaHs)a 50 100 ll 1 0 0 N-O CIHQ EXAMPLE 14 Sheep heavily infested with sheep keds (Melophagus Blowfly Test V ovinus) are dipped in these preparations of active com- Solvem: 35 parts by weight ethyleneglycol 15 pound. The sheep are observed 1, 8 and 28 days after monomethyl ether Emulsifier: 35 parts by weight nonylphenolpolyglycol ether To produce a suitable formulation, 3 parts by weight of active compound are mixed with 7 parts -of the abovementioned solvent-emulsifier mixture, and the emulsion concentrate so obtained is diluted with water to the concentration desired in each case.

1.5 ml of the formulation for application are pipetted on to a round filter paper with a diameter of 7.5 cm. After air-drying of this impregnated filter paper, this is transferred to a Petri dish. blowflies (Lucilia cuprina, strains normally sensitive to, and strains resistant to, phosphoric acid esters) are then put into the Petri dish and covered with a lid.

At various times after the treatment, the degree of destruction is determined; 100 percent means that all the flies, and 0 percent denotes that none of the flies,

have been killed.

The active compound investigated, the concentrations tried, the parasites tested and the findings obtained can be seen from the following Table 13:

monomethyl ether Emulsifier: parts by weight nonylphenolpolyglycol ether To produce a suitable formulation, 3 parts by weight of active compound are mixed with 7 parts of the abovementioned solvent-emulsifier mixture, and the emulsion concentrate so obtained is diluted with water to the concentration desired in each case.

application of the active compound and the number of living and dead sheep keds is ascertained.

At various times after the the treatment, the degree of destruction is determined; percent means that all the keds, and 0 percent denotes that none of the keds, have been killed.

The active compound investigated, the concentrations tried, the parasite tested and the findings obtained can be seen from the following Table 14:

TABLE 14 (Sheep ked test) Active compound Parasite Concentration Effect in A of active comafter days pound in ppm 1 8 28 @p-o-mo c1115):

Melo- 1000 100 100 100 phagus 750 100 100 100 ovinus 500 100 I00 100 EXAMPLE 16 Critical Concentration Test/Soil Insects Test insect: Phorbia brassicae maggots in the soil Solvent: 3 parts by weight acetone Emulsifier: 1 part by weight alkylarylopolyglycol ether To produce a suitable preparation of active compound, part by weight of active compound is mixed with the stated amount of solvent, the stated amount of emulsifier is added and the concentrate is diluted with water to the desired concentration. The preparation of active compound is intimately mixed with soil. The concentration of the active compound in the preparation is of practically no importance; only the amount of active compound per unit volume of soil, which is given in p.p.m. (for example mg/l), is decisive. The soil is filled into pots and the pots are left to stand at room temperature. After 24 hours, the test animals are put into the treated soil and, after a further 48 hours, the degree of effectiveness of the active compound is determined as a percentage by counting the dead and living test insects. The degree of destruction is 100 percent when all the test insects have been killed; it is 0 percent when exactly as many test insects are still alive as in the case of the control.

The active compounds, the amounts applied and the results can be seen from the following Table I5.

TABLE 15.SOIL INSECTICIDES [Phorbia brassicae maggots in the soil] Degree of Concentration of active destruction compound in p.p.m. in percent Active compound 10 5 2. 5 1. 0. 625

(1) i 100 100 100 100 100 so C0P(0C H NOC7H5 Q-c-o-mocnm N-omm V (31) fi/CZHE 100 100 100 100 95 [I N-OCH; OCiHS (6) fi/CiH!) 100 100 100 100 100 100 NOCH; 00,115

- :0-P o 01m):

N-OCH:

Cl-Q-(fi-O-P o 0:115):

N-OC H;

c-o-P 0c,m),

NOC:H5 c1 (9) II 100 100 100 r00 50 -C-OP(OC:H5):

N-OC2H5 c1 C 0P(0c,mn N-OCQH; Br

HaCfi-OP(O 01m):

OzNQ-(flJ-O-HOCQHQ:

N-O C7115 ll NO 01H, OCgH ll/ OzN- -C0-P ll I NOCgHs OCgHs fi-SP(OCIH5)7 N-CH:

(known) EXAMPLE 17 Emulsifier: 1 part by weight alkylarylpolyglycol ether 1 To produce a suitable preparation of active com- -Critical Concentration Test/Soil Insects 65 pound, 1 part by weight of active compound is mixed Test Insect: Tenebrio Molitor larvae with the stated amount of solvent, the stated amount of Solvent: 3 parts by weight acetone emulsifier is added and the concentrate is diluted with water to the desired concentration. The preparation of active compound is intimately mixed with soil. The concentration of the active compound in the preparation is of practically no importance; only the amount of active compound per unit volume of soil, which is given in p.p.m. (for example mg/l), is decisive. The soil is filled into pots and the pots are left to stand at room temperature. After 24 hours, the test animals are put into the treated soil and, after a further 48 hours, the degree of effectiveness of the active compound is determined as a percentage by counting the dead and living test insects. The degree of destruction is 100 percent when all the test insects have been killed; it is percent when exactly as many test insects are still alive as in the case of the control.

The active compounds, the amounts applied and the results can be seen from the following Table TABLE Iii- SOIL INSECTICIDES Tenehrio molitor/larvae in the soil] Found 1 10.1%

Analogously, the following compounds are prepared:

Concentration of active compound in p.p.m.

Degree of I destruction in percent NO CgH5 O CzHa (known) The process of the present invention is illustrated in and by the following preparative Example.

EXAMPLE 18 S ll . 36.5 g (0.22 mole, m.p. 63C) of N-ethyloxybenzhydroxamic acid are dissolved in 150 cc of acetonitrile. After addition of 36 g (0.26 mole) of finely powdered potassium carbonate the mixture is heated to 50C for 30 minutes, with stirring; at this temperature, 37.5 g 65 (physical properties Yield refraction; m .p./b.p.)

Constitution theory) b.p. 94C/0.0l mm Hg pale yellow oil 73.6 b.p. l05C/0.01 mm Hg colorless oil b.p. 90C/0.0l mm Hg pale yellow oil I l-0011a b.p. lO3C/0.0l mm Hg pale yellow oil crystallization in ice water s 01H,

I IOCH: 00,135

m," l.5350 b.p. 95C/0.01 mm Hg yellow 011 S ClCO1 (O CzHs):

..,.. l I-O.C2H5

yellowish oil S CO-I (0 02m); $1 I I-O 02H.

pale yellow oil S Q-C-O-ILOCzHs):

(I:l I l-O (3 H;

orange-colored oil orange-colored oil n 1.5361 pale yellow oil m.p. 78C light-yellow needles N-O CH:

yellowish oil orange-colored 011 n 1.5260 orange-colored 011 n 1.5148 orange-colored oil NOCH:

m, 1.5440 yellowish oil NOCzHs m, 1.5332 orange-colored oil (In N-OCH:

u 1.5469 orange-colored oil $1 OCH:

a 1.5496 orange-colored oil N-O CH3 m, 1.5537 orange-colored oil m," 1.5352 clear yellow oil The other compounds specifically mentioned in the test Examples may also be prepared by processes analogous to that given above in Example 1.

It will be appreciated that the instant specification and examples are set forth by way of illustration and not limitation, and that various modifications and changes may be made without departing from the spirit and scope of the present invention,

What is claimed is:

l. O-(N-alkoxy-benzimidoyl)-(thiono)phosphoric(- phosphonic) acid esters of the general formula N oR R X alkyl or alkoxy radical with one to four carbon atoms; R is methyl, ethyl or nor isopropyl; n is l or 2, and Y is chlorine, bromine, methyl, ethyl or nitro.

3. The compound according to claim I wherein such 5 compound is 0-ethyl-0-(N-methoxybenzimidoyl)- ethanethionophosphonic acid ester of the formula 02m r-* N0CHa O Calls 4. The compound according to claim 1 wherein such compound is 0,0-diethyl-0-( N-ethoxy-4- nitrobenzimidoyl)-thionophosphoric acid ester of the formula 5. The compound according to claim 1 wherein such compound is 0-ethyl-0-(N-ethoxy-4-nitrobenzimidoyl)- ethanethionophosphonic acid ester of the formula 6. The compound according to claim 1 wherein such compound is 0,0-dimethyl-Q-(N-ethoxy-2- chlorobenzimidoyl)-thionophosphoric acid ester of the 7. The compound according to claim 1 wherein such compound is 0,0-dimethyl-0-(N-ethoxy-2- bromobenzimidoyl)-thionophosphoric acid ester of the formula r f "Col. 2,.line ll, change "It" to --If--;

MW e Um'rmn s'm'uss lA'lEN'l OFFICE t 1 r 1' r 1 1 ChRFHHCAlLjQb CORRECTTON fratent 3,760,041 Dated September 18; 1973 Invencor(e) Walter Lorenz er a1 It 1e certified that error appearsdn the aboye-identified patent and that said Letters Patent are hereby corrected as shown below:

line 40, correct spelling of "mentioned"; 7 line 51, change Qethyl to O-etnyl Col. 6, line 38, change hydro carbons" to -hydrocarbons--. Col: 21, line llr'efcer "Example" insert ll--o Col, 21, Table 10, Compound (2), change "(OCH to --(OCH Cola; 21,22, Iable 10, Compound (9) last column, delete "100", I second occurrence. 0018; 2l,'22, Table 10, Compound 10 last column, change "3509 to 50 third occurrence. Cols. 27, 28, Table 15, Compound (12), under heading "0.625", delec Compound (13), under heading 90.625" inserc 50 I Col. 29, Table 16, in the heading insert before Tenebrio Col. 33, Compound (28), correct formula to read:

Signed and sealed this 29th day of October 1974.

(SEAL) Attest:

Mead M,-GIBSONJR. C c. MARSHALL DANN Attesting Officer Commiesioner of Patents 

2. Compounds according to claim 1, in which R is a straight-chain or branched alkyl radical with one to four carbon atoms, R1 is a straight-chain or branched alkyl or alkoxy radical with one to four carbon atoms; R2 is methyl, ethyl or n- or isopropyl; n is 1 or 2, and Y is chlorine, bromine, methyl, ethyl or nitro.
 3. The compound according to claim 1 wherein such compound is 0-ethyl-0-(N-methoxybenzimidoyl)-ethanethionophosphonic acid ester of the formula
 4. The compound according to claim 1 wherein such compound is 0, 0-diethyl-0-(N-ethoxy-4-nitrobenzimidoyl)-thionophosphoric acid ester of the formula
 5. The compound according to claim 1 wherein such compound is 0-ethyl-0-(N-ethoxy-4-nitrobenzimidoyl)-ethanethionophosphonic acid ester of the formula
 6. The compound according to claim 1 wherein such compound is 0, 0-dimethyl-0-(N-ethoxy-2-chlorobenzimidoyl)-thionophosphoric acid ester of the formula
 7. The compound according to claim 1 wherein such compound is 0, 0-dimethyl-0-(N-ethoxy-2-bromobenzimidoyl)-thionophosphoric acid ester of the formula 